Thermoplastic elastomer composition, insulating glass using the composition, process for producing the insulating glass and nozzle for producing the insulating glass

ABSTRACT

A thermoplastic elastomer composition produced from a thermoplastic resin and rubber and having a dispersion phase formed of a rubber composition at least part of which is dynamically crosslinked in the continuous phase of the thermoplastic resin, insulating glass using the thermoplastic elastomer composition as a sealing material and spacer, a process for producing the insulating glass using a sealing material made from the thermoplastic elastomer composition, comprising the steps of inserting the leading end of a charging nozzle into a space between the peripheral portions of a plurality of glass sheets, discharging the sealing material from the leading end of the nozzle body at a predetermined rate, and moving the glass sheets or the nozzle body relative to each other to charge the sealing material made from the thermoplastic elastomer composition into the space between the peripheral portions of the glass sheets, and a nozzle used in this process.

This application is a divisional application of Ser. No. 09/639,889filed Oct. 19, 1999, now U.S. Pat. No. 6,491,992.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a thermoplastic elastomer compositionhaving excellent steam permeation resistance and heat distortionresistance, insulating glass using the composition as a sealing materialand spacer, a process for producing the insulating glass and a nozzlefor producing the insulating glass.

2. Prior Art

Heretofore, there has been known insulating glass constituted such thata sealing material having a predetermined width is charged into a spacebetween the peripheral portions of at least two glass sheets which areopposed to each other in parallel and the hollow layer between the glasssheets is isolated from the outside air for the purpose of animprovement of heat insulating properties, dew condensation preventionproperties and the like.

This insulating glass has been produced as follows, for example. Asshown in FIG. 7, an aluminum spacer 73 filled with a desiccating agent72 is placed in a space between the peripheral portions of two glasssheets 71 a and 71 b which are opposed to each other in parallel andheld by a jig or the like to fix a predetermined interval between theglass sheets. Thereafter, a primary sealing material 74 is charged intospaces between the both side surfaces of the spacer 73 and the glasssheets 71 a and 71 b, and a two-liquid mixing and normal temperaturecurable type secondary sealing material 75, for example by apolysulfide- or silicone-based sealing material, is charged into a spacebetween the spacer 73 and the opening side of the glass sheets 71 and 71b.

Japanese Patent Application Laid-Open No. Hei 10-158041 discloses ainsulating glass production process and apparatus. In the process andapparatus, a plurality of glass sheets are held in a perpendiculardirection so that the plurality of glass sheets can be simultaneouslymoved in the same direction at the same speed, the glass sheets and adie are moved in different unidirections which are perpendicular to eachother, the glass sheets and the die are moved relative to each otheralternately such that the glass sheets are stopped when the die ismoved, and vice versa, and a resin material is extruded onto theperipheral portions of the glass sheets opposed to each other by movingthe glass sheets and the die alternately for each side of the glasssheets.

However, since the former production process is carried out by using ajig, spacer and the like, the work becomes complicated and takes muchtime and labor. On the other hand, the latter process has such a problemthat it is difficult to obtain insulating glass having good appearancebecause the resin material cannot be paved nicely when it is extruded.

In the insulating glass using the normal temperature curable sealingmaterial in the prior art processes, it takes time to cure the sealingmaterial and a final product cannot be promptly shipped. Especially inwinter, the sealing material must be placed in a heating chamber forcuring.

Therefore, it is desired to improve productivity by simplifying theprocess for producing insulating glass and shortening the cure time.

In contrast to this, Japanese Patent Application Laid-Open Nos. Hei10-110072, Hei 10-114551, Hei 10-114552 and the like propose aninvention in which a resin containing a desiccating agent as required isused as a spacer and sealing material in place of the aluminum spacer.The spacer/sealing material proposed in these publications is acomposition containing butyl-based rubber and crystalline polyolefinwhich are preferably mixed at a high temperature.

In insulating glass using this composition, the composition serves as aresin spacer and a sealing material. Insulating glass can be produced inwhich the peripheral portions of the glass sheets are sealed up bypaving the composition on the peripheral portions of two glass sheetsopposed to each other with a spacer therebetween. Thus, the productionprocess is simplified. However, in this insulating glass, the glasssheets are not dislocated each other when a load is placed upon theglass sheets at normal temperature but the glass sheets are dislocatedeach other while a high-temperature sealing material is paved and curedespecially when the insulating glass is produced or when the temperatureof the outside air rises in summer or by sunlight after the insulatingglass is formed into a construction material or the like because thecomposition which serves as a sealing material and resin spacer containsa small amount of a resin in rubber and hence, is easily deformed athigh temperatures.

SUMMARY OF THE INVENTION

It is a first object of the present invention to provide a thermoplasticelastomer composition which has excellent steam permeation resistanceand heat distortion resistance and is suitable for use as a sealingmaterial and spacer for insulating glass.

It is a second object of the present invention to provide insulatingglass which uses the thermoplastic elastomer composition as a sealingmaterial and spacer, is produced easily, has excellent steam permeationresistance and is not deformed in the entire shape by the dislocation ofthe glass sheets when it is allowed to cool after the sealing materialand spacer is paved, or after processing or at high temperatures insummer or the like.

It is a third object of the present invention to provide a process forproducing insulating glass which enables a sealing material to beefficiently paved in a space between the peripheral portions of glasssheets and leveled to obtain good appearance and reduces the number ofworking steps to carry out efficient work.

It is a fourth object of the present invention to provide a nozzle forproducing insulating glass which can be advantageously used in the aboveprocess for producing insulating glass.

The inventor of the present invention has conducted intensive studies tosolve the above problems and have found that the above objects can beattained by a thermoplastic elastomer composition containing acontinuous phase formed of a thermoplastic resin having a water vaporpermeability below a predetermined value and a dispersion phase formedby dynamically crosslinking a rubber component having a water vaporpermeability below a predetermined value after crosslinking, andinsulating glass using the composition as a sealing material and spacer.Thus, the present invention has been accomplished based on this finding.

To attain the first object, the present invention provides athermoplastic elastomer composition which is produced from athermoplastic resin having a water vapor permeability of 100 g/m²·24 hor less (30 μm in thickness) and rubber having a water vaporpermeability of 300 g/m²·24 h or less (30 μm in thickness) whencrosslinked and which has a dispersion phase formed of a rubbercomposition at least part of which is dynamically crosslinked in thecontinuous phase of the thermoplastic resin.

To attain the second object, the present invention provides insulatingglass which uses the thermoplastic elastomer composition as a sealingmaterial and spacer.

To attain the third object, the present invention provides a process forproducing insulating glass by charging a sealing material having apredetermined width into a space between the peripheral portions of atleast two glass sheets which are opposed to each other in parallel at apredetermined interval to isolate the hollow layer from the outside air,the process comprising the steps of inserting in advance the leading endof a charging nozzle into a space between the peripheral portions of aplurality of glass sheets, contacting a slide plate provided at the topof the leading end portion of the nozzle to the peripheral portions ofthe plurality of glass sheets, discharging a sealing material from theleading end of the nozzle body at a predetermined rate, and moving atleast one of the glass sheets and the nozzle body relative to the otherto charge the sealing material from the leading end portion of thenozzle into the space between the peripheral portions of the glasssheets.

To attain the fourth object, the present invention provides a nozzle forproducing insulating glass by inserting the leading end portion of thenozzle into a space between the peripheral portions of at least twoglass sheets which are opposed to each other in parallel at apredetermined interval, and charging a sealing material from the leadingend portion of the nozzle into the space between the peripheral portionsof the glass sheets while at least one of the glass sheets and thenozzle body is moved relative to the other, wherein the leading end ofthe nozzle body has a width for positioning the interval between theplurality of glass sheets, and a slide plate which slides along theperipheral portions of the plurality of glass sheets and is provided atthe top of the leading end portion.

BRIEF DESCRIPTION OF THE DRAWINGS

These and further features of the present invention will be apparentwith reference to the following description and drawings, wherein:

FIGS. 1(a) and (b) are schematic sectional views of insulating glassaccording to an embodiment of the present invention;

FIG. 2 is a perspective view of a nozzle for producing insulating glassof the present invention;

FIG. 3 is a side view of the nozzle for producing insulating glass ofthe present invention;

FIG. 4 is a plan view of the nozzle for producing insulating glass ofthe present invention;

FIG. 5 is a perspective view showing that a sealing material is chargedinto a space between the peripheral portions of two glass sheets;

FIG. 6 is a sectional view of a cup for measuring water vaporpermeability; and

FIG. 7 is a diagram for explaining the insulating glass productionprocess of the prior art.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be described in detail hereinunder.

The thermoplastic elastomer composition of the present invention (to bereferred to as “composition of the present invention” hereinafter) issuitable for use as a sealing material and spacer for insulating glassand has a continuous phase formed of a thermoplastic resin and adispersion phase formed of a rubber composition at least part of whichis dynamically crosslinked. The dispersion phase is uniformly dispersedin the continuous phase.

A thermoplastic resin having a water vapor permeability of 100 g/m²·24 hor less when a sheet having a thickness of 30 μm is formed from thethermoplastic resin alone is used as the thermoplastic resin which isone of the components of the composition of the present invention.

Illustrative examples of the thermoplastic resin includepolyolefin-based resins such as high-density polyethylene (HDPE),low-density polyethylene (LDPE), ultra high molecular weightpolyethylene (UHMWPE), isotactic polypropylene, syndiotacticpolypropylene and ethylene-propylene copolymer resins; polyamide-basedresins such as nylon 6 (N6), nylon 66 (N66), nylon 46 (N46), nylon 11(N11), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), nylon 6/66copolymer (N6/66), nylon 6/66/610 copolymer (N6/66/610), nylon MXD6(MXD6), nylon 6T, nylon 6/6T copolymer, nylon 66/PP copolymer and nylon66/PPS copolymer; polyester-based resins such as aromatic polyestersexemplified by polybutylene terephthalate (PBT) and polyethyleneterephthalate (PET); polyether-based resins such as polyphenylene oxide(PPO), modified polyphenylene oxide (modified PPO), polysulfone (PSF)and polyether ether ketone (PEEK); polymethacrylate-based resins such asmethyl polymethacrylate (PMMA) and ethyl polymethacrylate;polyvinyl-based resins such as a vinyl alcohol/ethylene copolymer(EVOH), polyvinylidene chloride (PVDC) and vinylidene chloride/methylacrylate copolymer; fluororesins such as polyvinylidene fluoride (PVDF),polychlorofluoroethylene (PCTFE) and polyacrylonitrile resin (PAN); andthe like.

Out of these, polyolefin-based resins, polyester-based resin,polyether-based resin and fluororesins having a heat distortiontemperature of 50° C. or more are preferred because the composition ofthe present invention obtained therefrom has excellent moldability andexcellent heat distortion resistance against the temperature of theoutside air or the like when it is used as a sealing material and spacerfor insulating glass which will be described hereinafter, so that areduction in water vapor permeability caused by water absorption can beminimized.

The dispersion phase dispersed in the continuous phase of thecomposition of the present invention is formed of a rubber compositionat least part of which is dynamically crosslinked. Rubber having a watervapor permeability of 300 g/m²·24 h or less when a sheet having athickness of 30 μm is produced by crosslinking only a rubber componentis used as a rubber component which is the main constituent ingredientof this dispersion phase. Illustrative examples of the rubber componentinclude cyclic NR, ethylene propylene rubber (EPDM, EPM),polyisobutylene, IIR, Br-IIR, CI-IIR, halide of a paramethylstyrene-polyisobutylene copolymer (X-IPMS), ethylene-vinyl acetaterubber (EVA), chlorinated polyethylene, chlorosulfonated polyethylene,acrylonitrile butadiene rubber and hydride thereof, hydrin rubber andthe like. Out of these, ethylene propylene rubber, IIR, Br-IIR andX-IPMS are preferred from the viewpoints of heat resistance at the timeof kneading with a resin, low water vapor permeability and crosslinkingreactivity.

Further, a reinforcement, filler, softening agent, crosslinking agent,age resistor, processing aid and the like which are generally blended toimprove the dispersibility, heat resistance and the like of the rubbercomposition and for other purposes may be suitably blended into therubber composition forming the dispersion phase.

A combination of a thermoplastic resin forming the continuous phase andrubber which is the main constituent ingredient of the dispersion phaseof the composition of the present invention is not particularly limitedand at least one thermoplastic resin selected from the abovethermoplastic resins and at least one rubber selected from the aboverubbers may be used in combination.

The weight ratio of the thermoplastic resin composition to the rubbercomposition constituting the composition of the present invention is notparticularly limited but preferably 85/15 to 15/85, more preferably50/50 to 30/70.

The criticality of this ratio is dependent upon the volume ratio andviscosity ratio of the thermoplastic resin composition to the rubbercomposition.

The rubber composition is the dispersion phase and the thermoplasticresin composition is the continuous phase of the composition of thepresent invention. Even when the both components are simply kneadedtogether while they are molten, a thermoplastic elastomer compositionhaving a dispersion structure of interest is not always obtained. Therelationship between the melt viscosity of the thermoplastic resincomposition to the melt viscosity of the rubber component at theirkneading temperature is adjusted by controlling the volume ratio of theboth components to be blended so that the value of α₁ obtained from thefollowing equation should become less than 1.α₁=(φ_(R)/φ_(P))×(η_(P)/η_(R))where Φ_(R) is the volume fraction of the rubber composition, φ_(P) isthe volume fraction of the thermoplastic resin composition, η_(P) is themelt viscosity (poise) of the rubber composition at a temperature and ashearing speed at which the thermoplastic resin composition and therubber composition are kneaded together, and η_(R) is the melt viscosity(poise) of the thermoplastic resin composition at a temperature and ashearing speed at which the thermoplastic resin composition and therubber composition are kneaded together.

When the value of α₁ is 1 or more, the dispersion structure of thecomposition of the present invention may be inverted and the rubbercomposition may be the continuous phase of the composition.

0.5≦η_(R)/η_(P)≦3.0 is preferred. Within this range, the rubbercomposition is dispersed in the thermoplastic resin as particles havinga size of about 0.1 μm to several tens of μm.

In the present invention, the term “melt viscosity” means the meltviscosity of each component at an arbitrary temperature when it iskneaded. Since the melt viscosity of a polymer component changesaccording to temperature, shearing speed (sec⁻¹) and shearing stress, itis obtained from the following equation by flowing the polymer componentin a molten state in a thin tube at an arbitrary temperature at whichthe component is molten, particularly at a temperature range at the timeof kneading and measuring stress and shearing speed.

 η=σ/{dot over (γ)}

where σ is a shearing stress and {dot over (γ)} is a shearing speed.

The capillary rheometer capillograph 1C of Toyo Seiki Co., Ltd. may beused as an example for the measurement of melt viscosity.

The composition of the present invention may contain a moistureabsorbent. When the composition of the present invention is used as asealing material or spacer for insulating glass, particularly a sealingmaterial and spacer, it preferably contains a moisture absorbent.

The expression “sealing material and spacer” means that the compositionof the present invention is used as a spacer arranged in a space betweenthe peripheral portions of the opposed glass sheets of insulating glassto ensure the thickness of an air layer for the insulating glass andthat the spacer is press-contacted to the glass sheets without paving asealing material between the spacer and the glass sheets so that thecomposition of the present invention is used as a sealing material forisolating the air layer from the outside air. That is, when thecomposition of the present invention is used as a sealing material andspacer, it serves as a spacer and a sealing material at the same time.

The composition of the present invention may be used as a sealingmaterial for insulating glass and used in combination with other spacer,or may be used as a spacer and used in combination with other sealingmaterial.

The composition of the present invention preferably contains a moistureabsorbent. When the composition of the present invention is used as asealing material and spacer for insulating glass, it is effectivebecause it can absorb moisture contained in the air layer formed betweenthe two glass sheets, dry the air layer, absorb water entering from theoutside of the insulating glass and prevent a rise in the dew point ofair sealed in the air layer. The expression “dew point in the insulatingglass” means the highest temperature at which dew condensation on theinner surface of the insulating glass is visually observed.

A moisture absorbent which is generally charged in the metal spacer orthe like of insulating glass may be used as the moisture absorbent, asexemplified by synthetic zeolite, silica gel, alumina and the like.

The amount of the moisture absorbent is preferably 10 to 70 parts byweight based on 100 parts by weight of the total of polymer components(a thermoplastic resin and rubber) of the present invention. Within thisrange, a composition having excellent hygroscopicity can be obtained.

Further, the composition of the present invention preferably contains asteam permeable barrier resin (to be referred to as “barrier resin”hereinafter). The composition of the present invention has excellentsteam permeation resistance because the thermoplastic resin which is thecontinuous phase of the composition and rubber which is the mainconstituent ingredient of the dispersion phase have a water vaporpermeability below respective predetermined values. However, when thecomposition of the present invention contains a barrier resin, the steampermeation resistance of the obtained composition of the presentinvention is further improved.

The term “barrier resin” used herein means a resin which has a smallerwater vapor permeability than that of the thermoplastic resin which isthe continuous phase, can be a barrier by increasing its crystallinityeven if it is the same type of a resin as the thermoplastic resin of thecontinuous phase, which is preferably kneaded into the continuous phasein layers in a lamellar form when it is kneaded into the thermoplasticelastomer composition of the present invention and which is desirablylamellar in shape with an aspect ratio of 10 to 500 (aspect ratio: a/bwhere a is the length of a long axis and b is the length of a shortaxis).

In insulating glass which uses the composition of the present inventionas a sealing material and spacer which will be described hereinafter,the barrier resin is preferably existent in the continuous phase of thecomposition of the present invention and dispersed as a lamellar productparallel to the peripheral surfaces of the insulating glass. The barrierresin dispersed in layers is effective in preventing the permeation ofsteam and reducing water vapor permeability.

Illustrative examples of a resin component constituting the barrierresin include polyolefins such as high-density polyethylene (HDPE) andultra high molecular weight polyethylene (UHMWPE), polyamide resins suchas nylon 6, nylon 66 and aromatic nylon (MXD6), polyester resins such aspolyethylene terephthalate (PET), polyvinyl resins such asethylene-vinyl alcohol (EVOH), polyvinyl chloride resins, polyvinylidenechloride (PVDC) resins and the like. In the present invention, thesebarrier resins may be used alone or in combination of two or more.

When the composition of the present invention contains a barrier resin,the content of the barrier resin is suitably determined such that themelt viscosities and volume fractions of the thermoplastic elastomercomposition which is the composition of the present invention excludingthe barrier resin, and the barrier resin should satisfy the followingexpressions (1) and (2). The weight ratio of the above thermoplasticelastomer composition to the barrier resin is generally 90/10 to 50/50,particularly preferably 90/10 to 70/30.

 η_(d)/η_(m)≧2.0  (1)α₂=Φ_(d)/Φ_(m)×η_(m)/η_(d)<1.0  (2)where η_(d) is the melt viscosity (poise) of the barrier resin, η_(m) isthe melt viscosity (poise) of the thermoplastic elastomer composition,Φ_(d) is the volume fraction of the barrier resin, and Φ_(m) is thevolume fraction of the thermoplastic elastomer composition.

In the expression (1), when the value of η_(d)/η_(m) is less than 2, thebarrier resin is finely dispersed in the thermoplastic elastomercomposition while it is molten and kneaded and its function as a barrierbecomes reduced. The value of η_(d)/η_(m) is preferably 3 or more. Inthe expression (2), when α₂ is less than 1, the barrier resin can beexistent as a dispersion phase in the continuous phase formed of thethermoplastic elastomer composition, more specifically, in thethermoplastic resin composition forming the continuous phase of thethermoplastic elastomer composition.

A filler such as talc, calcium carbonate, mica or carbon black,tackifier such as rosin ester and coumarone resin, age resistor, thermalstabilizer, antioxidant, softening agent, processing aid agent and otheradditives may be added to the composition of the present invention inlimits that do not impair the object of the present invention in orderto improve fluidity, heat resistance, physical strength, costperformance and the like. Further, an inorganic pigment and organicpigment may be blended into the thermoplastic resin composition forcoloration.

Moreover, an adhesion promoter may be added to the composition of thepresent invention to improve adhesion to glass. The adhesion promoter isa silane coupling agent such as vinylsilane, methacrylsilane,aminosilane, epoxysilane or mercaptosilane, or a polymer having a maleicacid group, carboxylic acid group, hydroxyl group or epoxy group.Specific examples of the adhesion promoter include maleic acid modifiedpolyethylene, maleic acid modified polypropylene, maleic acid modifiedethylene ethyl acrylate, epoxy modified styrene-butadiene copolymer,epoxy modified ethylene-vinyl acetate copolymer, ethylene-vinyl acetatecopolymer and saponified products thereof.

When the chemical compatibilities of the above specific thermoplasticresin composition and rubber composition are different from each other,an appropriate compatibilizing agent is preferably used as a thirdcomponent to compatibilize the both materials. The interfacial tensionbetween the thermoplastic resin composition and the rubber compositionis reduced by mixing a compatibilizing agent, with the result that thecharacteristic properties of the both compositions are developed moreeffectively as the particle diameter of the rubber composition formingthe dispersion phase becomes very small. The compatibilizing agent isgenerally a copolymer having both structures of a resin component and arubber component or either one of them, or a copolymer having an epoxygroup, carboxyl group, carbonyl group, halogen group, amino group,oxazoline group or hydroxyl group which can react with a resin componentor rubber component. They can be selected according to the types of theresin component and the rubber component to be mixed together.

General-purpose compatibilizing agents include astyrene-ethylene-butylene-styrene-based block copolymer (SEBS) andmaleic acid modified product thereof, EPDM, EPM and maleic acid modifiedproducts thereof, EPDM/styrene and EPDM/acrylonitrile graft copolymerand maleic acid modified products thereof, styrene/maleic acidcopolymer, reactive phenoxthine and the like.

When a compatibilizing agent is blended into the composition of thepresent invention, its amount is not particularly limited but preferably0.5 to 20 parts by weight based on 100 parts by weight of the total ofpolymer components (the thermoplastic resin and rubber).

In the present invention, a vulcanizing agent, vulcanizing accelerator,vulcanization conditions (temperature and time) and the like used forthe dynamic crosslinking of the rubber composition may be suitablydetermined according to the composition of the rubber composition usedand are not particularly limited. A general rubber vulcanizing agent(crosslinking agent) may be used as the vulcanizing agent.

Illustrative examples of sulfur-based vulcanizing agents used as therubber vulcanizing agent include powdery sulfur, precipitating sulfur,highly dispersible sulfur, surface treated sulfur, insoluble sulfur,dimorpholine sulfide, alkylphenol disulfide and the like.

When this sulfur-based vulcanizing agent is used, its amount ispreferably 0.5 to 4 phr (parts by weight based on 100 parts by weight ofthe rubber component, this shall apply thereafter).

Organic peroxide-based vulcanizing agents include benzoyl peroxide,t-butylhydro peroxide, 2,4-dichlorobenzoyl peroxide,2,5-dimethyl-2,5-di(t-butylperoxy)hexane and2,5-dimethylhexane-2,5-di(peroxybenzoate).

When this organic peroxide-based vulcanizing agent is used, its amountis preferably 1 to 15 phr.

Further, phenol resin-based vulcanizing agents include bromides ofalkylphenol resins, mixed crosslinking vulcanizing agents containing ahalogen doner such as tin chloride or chloroprene and an alkylphenolresin.

When this phenol resin-based vulcanizing agent is used, its amount ispreferably 1 to 20 phr.

Other vulcanizing agents include zinc oxide (about 5 phr), magnesiumoxide (about 4 phr), litharge (about 10 to 20 phr), p-quinone dioxime,p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone,poly-p-dinitrosobenzene (about 2 to 10 phr) and methylindianiline (about0.2 to 10 phr).

The composition of the present invention may contain a vulcanizingaccelerator as required. A general vulcanizing accelerator such asaldehyde-ammonia-based, guanidine-based, thiazole-based,sulfenamide-based, thiuram-based, dithionate-based or thiourea-basedgeneral vulcanizing accelerator may be used in an amount of about 0.5 to2 phr.

Illustrative examples of the vulcanizing accelerator includehexamethylenetetramine as the aldehyde-ammonia-based vulcanizingaccelerator, diphenylguanidine as the guanidine-based vulcanizingaccelerator, dibenzothiazyldisulfide (DM), 2-mercaptobenzothiazole andZn salts and cyclohexylamine salts thereof as the thiazole-basedvulcanizing accelerator, cyclohexylbenzothiazyl sulfenamide (CBS),N-oxydiethylenebenzothiazyl-2-sulfenamide, N-t-butyl-2-benzothiazolesulfenamide and 2-(thymolpolynildithio)benzothiazole as thesulfenamide-based vulcanizing accelerator, tetramethylthiuram disulfide(TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide(TMTM) and dipentamethylenethiuram tetrasulfide as the thiuram-basedvulcanizing accelerator, Zn-dimethyl dithiocarbamate, Zn-diethyldithiocarbamate, Zn-di-n-butyl dithiocarbamate, Zn-ethylphenyldithiocarbamate, Tc-diethyl dithiocarbamate, Cu-dimethyldithiocarbamate, Fe-dimethyl dithiocarbamate and pipecolinepipecolyldithiocarbamate as the dithionate-based vulcanizing accelerator, andethylene thiourea and diethyl thiourea as the thiourea-based vulcanizingaccelerator.

A general rubber auxiliary such as zinc oxide (about 5 phr), stearicacid, oleic acid or Zn salt thereof (about 2 to 4 phr) may also be usedas the vulcanizing accelerator.

The composition of the present invention is prepared by previouslysupplying a thermoplastic resin component and an unvulcanized rubbercomposition to a kneader such as a double-screw kneader to melt andknead these compositions and dispersing the rubber composition in thethermoplastic resin composition forming a continuous phase (matrixphase) as a dispersion phase (domain). Thereafter, a thermoplasticelastomer composition can be produced by adding a vulcanizing agentunder kneading to dynamically crosslink the rubber composition. Theaddition of compounding additives to the thermoplastic resin compositionor rubber composition may be carried out during kneading but preferablycarried out before kneading. A vulcanizing agent is mixed into therubber composition in advance so that the rubber composition can becrosslinked while the thermoplastic resin composition and the rubbercomposition are kneaded together.

The kneader used for the kneading of the thermoplastic resin compositionand the rubber composition is not particularly limited and a screwextruder, kneader, Banbury mixer, double-screw kneading extruder and thelike may be used. Particularly for the kneading of the thermoplasticresin composition and the rubber composition and the dynamiccrosslinking of the rubber composition, a double-screw kneading extruderis preferably used. Two or more kneaders may be used to knead thesecompositions sequentially.

As for melt kneading conditions, the temperature may be higher than themelting temperature of the thermoplastic resin. When a barrier resin isblended, the temperature may be higher than the melting temperature ofthe thermoplastic resin and lower than the heat distortion temperatureof the barrier resin. The shearing speed at the time of kneading ispreferably 500 to 7,500 sec⁻¹. The total kneading time is 30 seconds to10 minutes and the vulcanizing time after addition is preferably 15seconds to 5 minutes.

The prepared thermoplastic elastomer composition is then extruded into astrand form from the kneading extruder, cooled with water or the like,pelletized by a pelletizer for resins and then may be molded. Thehigh-temperature thermoplastic elastomer composition thus prepared maybe directly paved and charged into a space surrounded by the peripheralportions of the glass sheets of the insulating glass and a previouslyinstalled spacer as a sealing material for the insulating glass.

Alternatively, the prepared thermoplastic elastomer composition may bemolded into the form of a spacer by extrusion molding, injection moldingor the like. In this case, when the high-temperature thermoplasticelastomer composition discharged from a molding machine is used,adhesion to the glass sheets and the spacer is advantageously increased.

When the composition of the present invention contains a barrier resin,pellets obtained by molding the thermoplastic elastomer compositionprepared as described above and the pellets of the above barrier resinare mixed in a predetermined ratio. The mixing of the pellets is carriedout by dry blending with a commonly used blender or the like, or bysupplying the pellets into a kneader from independent feeders in apredetermined ratio.

The mixture of the both pellets is melt kneaded at a low shearing speed(for example, 30 sec⁻¹ or more and less than 300 sec⁻¹), such that thethermoplastic elastomer composition and the barrier resin are meltkneaded in a single-screw extruder and the resulting mixture is extrudedfrom the end of the extruder or injection molded, and the resulting meltkneaded product is directly supplied into a molding machine to produce asealing material and spacer. Alternatively, the kneaded product may beextruded into a strand form from the end of the extruder, pelletized andmolded.

When the composition of the present invention is used as a sealingmaterial, spacer, or a sealing material and spacer, the barrier resin ispreferably aligned in lamellar layers parallel to the peripheralsurfaces of the insulating glass. In order to align the barrier resinlike this, it is effective to make flat the shape of the nozzle forextruding the composition of the present invention for injection or toset the shearing speed at the outlet of the extruder at 30 to 300 s⁻¹.

In the composition of the present invention obtained from the abovecomponents and by the above production process, the dynamicallycrosslinked rubber composition forms a dispersion phase in thethermoplastic resin composition forming a continuous phase. That is, inthe above production process, the crosslinking of the rubber compositionproceeds while the thermoplastic resin composition and the rubbercomposition are kneaded together so that the obtained compositioncontains the crosslinked rubber as a dispersion phase finely dispersedin the resin composition as a continuous phase.

In a composition obtained merely by kneading the thermoplastic resinwith rubber, rubber is dispersed as fine particles immediately afterthey are kneaded and provided with large shearing force but rubber turnsback to a large mass when kneading is stopped with the result that therubber may form a continuous phase and the thermoplastic resin may bedispersed in the rubber. A composition having this structure has lowheat distortion resistance because the rubber forms a continuous phase.

The composition of the present invention has excellent steam permeationresistance. The composition of the present invention in which rubber isfinely dispersed in the thermoplastic resin has also excellent heatdistortion resistance.

The composition of the present invention containing a moisture absorbenthas excellent hygroscopicity.

The composition of the present invention comprising a thermoplasticresin having a heat distortion temperature of 70° C. or more as acontinuous phase is excellent in heat distortion resistance and alsoprocessability when the composition of the present invention isprocessed into a sealing material or the like.

Further, the composition of the present invention containing a steampermeable barrier resin is more superior in steam permeation resistance.

A description is subsequently given of insulating glass which uses thecomposition of the present invention as a sealing material and spacer.

FIGS. 1(a) and 1(b) are schematic sectional views in a directionperpendicular to glass sheets of the insulating glass of the presentinvention. In the insulating glass 10 shown in FIGS. 1(a) and 1(b), aspacer 3 for determining the interval between two opposed glass sheets 1a and 1 b is installed between the two glass sheets 1 a and 1 b to forman air layer 2 having a predetermined volume therebetween. This spacer 3may be made from a metal such as aluminum and a sealing material madefrom the composition of the present invention may be installed as aseparate unit, but the spacer 3 is preferably made from the compositionof the present invention. The hardness of the spacer made from thecomposition of the present invention is 25 to 90 in terms of JIS Ahardness. Within this range, even when stress is applied to the adhesivesurfaces between the glass sheets and the spacer by a rise in thetemperature of the air layer 2, it can be avoided that the glass isbroken if bonding strength is high and the glass sheets and the spacerare separated from each other if bonding strength is insufficient.Further, within this range, the insulating glass is not deformed by theweight of the glass sheets.

The interval between the glass sheets 1 a and 1 b is generally about 6mm or about 12 mm. The insulating glass 10 shown in FIGS. 1(a) and 1(b)comprises two glass sheets. The number of the glass sheets is notlimited to two but two or more glass sheets may be used and the numberof the glass sheets can be selected as required.

In the insulating glass of the present invention shown in FIGS. 1(a) and1(b), the spacer 3 also serves as a sealing material for sealing up thespace between the two glass sheets 1 a and 1 b from the outside air andholding the glass sheets. The spacer 3 prevents water from entering fromthe outside without using a primary sealing material, a secondarysealing material and the like and serves as a spacer and sealingmaterial for holding the two glass sheets 1 a and 1 b at a predeterminedinterval.

The insulating glass of the present invention may have adhesive layers 4between the spacer 3 which also serves as a sealing material and theglass sheets 1 a and 1 b as shown in FIG. 1(b). When the insulatingglass of the present invention has the adhesive layers 4, adhesionbetween the spacer 3 and the glass sheet 1 a or 1 b can be improved, theentry of water from the outside of the insulating glass can beprevented, and a rise in the dew point of the air layer 2 can besuppressed.

A glass sheet for use in construction materials, vehicles or the likecan be used as the glass sheet of the insulating glass of the presentinvention, as exemplified by glass which is generally used in windows,reinforced glass, wire-net glass, heat absorbing glass, heat reflectingglass, organic glass and the like. The thickness of the glass sheet issuitably determined.

An adhesive used in the adhesive layer 4 is a silane coupling agent suchas vinylsilane, methacrylsilane, aminosilane, epoxysilane ormercaptosilane, or a polymer having a maleic acid group, carboxylic acidgroup, hydroxyl group, epoxy group or the like. Illustrative examples ofthe adhesive include maleic acid modified polyethylene, maleic acidmodified polypropylene, maleic acid modified ethylene ethyl acrylate,epoxy modified styrene-butadiene copolymer, epoxy modifiedethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer andsaponified products thereof. Out of these, olefin-vinyl acetatecopolymers are preferred. Illustrative examples of the olefin includeethylene, propylene, butene and the like. Out of these, anethylene-vinyl acetate copolymer is preferred from the viewpoint ofadhesion to glass and water resistance. The above olefin-vinyl acetatecopolymer is preferably saponified because the saponified product hashigh reactivity and improved adhesion.

The insulating glass of the present invention can be basically producedby extruding the composition of the present invention through a nozzleor the like connected to an extruder into a space between two fixedparallel glass sheets and bonding it to the glass sheets. The innersides of the peripheral portions of the glass sheets 1 a and 1 b towhich the spacer 3 is bonded can be coated with a primer as required andfurther an adhesive as required. As the case may be, the composition ofthe present invention is extruded onto the inner side of the peripheralportion of one of the two glass sheets and the other glass sheet ispress-bonded to the composition of the present invention before thecomposition does not become cool. To coat the primer and the adhesive,they may be coated manually with an applicator or the like, orautomatically using a robot for extruding the primer and the adhesive.

Particularly, the composition of the present invention and the adhesiveare co-extruded by an extruder such that the adhesive forms an outerlayer and the composition of the present inventor forms an inner layerand then molded into a spacer having a predetermined shape.Alternatively, the extruded composition of the present invention and theextruded adhesive may be directly discharged into the space between theperipheral portions of the glass sheets.

The composition of the present invention for forming a spacer, which hasa high temperature after kneading, is preferably used even when it ismolded into a spacer and installed between the glass sheets and evenwhen it is directly discharged into the space between the glass sheetsfrom an extruder. This is because strong adhesion between the spacer andthe glass sheets can be obtained.

The insulating glass of the present invention constituted as describedabove is produced very easily because the number of production steps isgreatly reduced compared with conventional insulating glass which isproduced using a metal spacer and a sealing material.

Since the composition of the present invention is used as a sealingmaterial and spacer, it does not take long to cure it unlike theconventional two-liquid type sealing material and hence, productivity ishigh. Since the composition of the present invention has excellent steampermeation resistance as described above, the insulating glass of thepresent invention has a low dew point. Further, since the composition ofthe present invention has excellent heat distortion resistance, evenwhen the temperature of the glass sheets becomes high due to thetemperature of the outside air or the like, the insulating glass is notdeformed by the dislocation of the glass sheets.

In the insulating glass which uses the composition of the presentinvention containing a moisture absorbent and a barrier resin, the airlayer can be held while it is dry, the entry of water from the outsidecan be prevented, and the dew point is maintained at a low level.

Further, out of the above processes for producing the insulating glassof the present invention, preferred is a process which comprises thesteps of inserting in advance the leading end of the charging nozzleinto the space between the peripheral portions of a plurality of glasssheets, contacting a slide plate provided at the top of the leading endportion of the nozzle to the peripheral portions of the plurality ofglass sheets, discharging a sealing material from the leading end of thenozzle body at a predetermined speed, and moving at least either one ofthe glass sheets and the nozzle body relative to the other to charge thesealing material into the space between the peripheral portions of theglass sheets from the leading end of the nozzle. According to thisprocess, the sealing material can be efficiently paved in the spacebetween the peripheral portions of the glass sheets and the sealingmaterial can be leveled to obtain good appearance, and efficient workcan be carried out by reducing the number of working steps.

Further, a production nozzle having a width for positioning the intervalbetween the plurality of glass sheets at the leading end of the nozzlebody and having a slide plate which slides along the peripheral portionsof the plurality of glass sheets at the top of the leading end portionis preferably used in this process.

This process will be described hereinunder with reference to FIGS. 2 to6.

FIG. 2 is a perspective view of a nozzle 20 for producing insulatingglass which is inserted between the peripheral portions of two glasssheets 1 a and 1 b which are opposed to each other in parallel and heldby an unshown jig or the like, FIG. 3 is a side view of the productionnozzle 20 and FIG. 4 is a plan view of the production nozzle 20.

The production nozzle 20 has a passage 12 for discharging a sealingmaterial W in a nozzle body 11 having an L-shaped section, at least theleading end portion 11 a of the nozzle 20 has a width H for positioningthe interval h between a plurality of glass sheets 1 a and 1 b, and aslide plate 13 which slides along the peripheral portions 1 x of theplurality of glass sheets 1 a and 1 b is integrally provided on theupper surface of the leading end portion 11 a.

The slide plate 13 projects along the discharge direction (directionshown by an arrow Q) of the sealing material W, and a guide plate 14 isformed at a lower end portion at the leading end of the nozzle body 20in such a manner that the guide plate 14 is substantially parallel tothe slide plate 13 and projects along the discharge direction of thesealing material W. The rear end portion 11 b of the nozzle body 11 isconnected to an unshown sealing material W feeder.

In the process for producing the insulating glass using this productionnozzle 20, as shown in FIG. 2, the leading end portion 11 a of thenozzle body 11 is first inserted into the space between the peripheralportions of two glass sheets 1 a and 1 b which are opposed to each otherin parallel at a predetermined interval and held by an unshown jig orthe like, and the sealing material W is charged into the space betweenthe peripheral portions of the glass sheets from the leading end portion11 a of the nozzle at a predetermined delivery pressure (for example, 15MPa) or a predetermined delivery rate (for example, 2,000 g/min) whileat least one of the glass sheets 1 a and 1 b and the nozzle body 11 ismoved relative to the other.

That is, the nozzle body 11 is moved along the peripheral portions 1 xof the glass sheets 1 a and 1 b while the glass sheets 1 a and 1 b arefixed at predetermined positions, or the glass sheets 1 a and 1 b aremoved at a predetermined speed while the nozzle body 11 is fixed. Or thenozzle body 11 and the glass sheets 1 a and 1 b are moved in oppositedirections at the same speed, while the sealing material W is suppliedinto the discharge passage 12 in the nozzle body 11 from the sealingmaterial W feeder and charged into the space between the peripheralportions of the glass sheets 1 a and 1 b.

When the sealing material W is charged while at least one of the glasssheets 1 a and 1 b and the nozzle body 11 is moved relative to theother, the slide plate 13 provided at the top of the leading end portionof the nozzle body 11 is contacted to the peripheral portions 1 x of theplurality of glass sheets 1 a and 1 b and slid (the sealing material Qis flatly pressed with a so-called knife), whereby the sealing materialW at the peripheral portions 1 x of the glass sheets 1 a and 1 b can beleveled, and at the same time, the lower side of the sealing material inthe space between the glass sheets 1 a and 1 b can be leveled by theguide plate 14 provided at the low end portion at the leading end of thenozzle body 11 as shown in FIG. 5.

The sealing material used in this process preferably has an MFR (meltflow rate) of 20 to 500 g/10 min.

According to the above process, the sealing material W can beefficiently paved in the space between the peripheral portions of theglass sheets 1 a and 1 b by charging the sealing material W into thespace between the peripheral portions of the glass sheets 1 a and 1 bfrom the leading end of the nozzle body 11 and leveled to obtain goodappearance, and efficient work can be carried out by reducing the numberof working steps.

In the above process, the method of charging the sealing material W intothe space between the two glass sheets 1 a and 1 b has been described.However, the sealing material W can be charged into spaces among two ormore glass sheets by transforming and processing the nozzle body 11.

EXAMPLE

The following examples are given to further illustrate the thermoplasticelastomer composition, insulating glass, a process for producing theinsulating glass and a nozzle of the present invention.

Examples 1 to 10 and Comparative Examples 1 and 2

Rubber shown in Table 1 was first pelletized by a rubber pelletizer atabout 100° C., and then rubber, a matrix resin, age resistor, filler andtackifier were dry blended in blending ratios for Examples 1 to 10 andComparative Examples 1 and 2, each of the resulting blends beinginjected into a double-screw kneader to be melt kneaded. Thereafter, anda vulcanizing agent was added from an intermediate injection port tocarry out dynamic vulcanization. At this point, the double-screw kneaderwas set at a temperature of 230° C. and a shearing speed of 1,000 s⁻¹.Further, a moisture absorbent and an adhesive promoter were injectedfrom a final injection port of the double-screw kneader.

A thermoplastic elastomer composition extruded into a strand form fromthe double-screw kneader was cooled with water and pelletized by a resinpelletizer.

Two square glass sheets having 300 mm per side were fixed in parallel toeach other at an interval of 6 mm, the above material was paved in aspace between the peripheral portions of the two glass sheets while itwas extruded from a nozzle and molded to form insulating glass. Thepellet was molded into a 30 μm-thick film by press molding as a sampleused for the measurement of water vapor permeability.

As for Examples 5 and 6, the thermoplastic elastomer compositionsprepared by the above method were dry blended with a barrier resinimmediately before extrusion molding for the formation of insulatingglass to form insulating glass by the same method as described above.

Comparative Example 3

Insulating glass was produced in the same manner as in the aboveExamples and Comparative Examples except that a vulcanizing agent forrubber was not added during blending.

(1) Water Vapor Permeability

Six liters of water which is half the volume of a stainless steel cup 60shown in FIG. 6 is injected into the stainless steel cup 60. An upperopening in the cup 60 is covered with a sample sheet 63 (30 μm inthickness) obtained by cutting the sample sheet obtained in Examples 1to 10 and Comparative Examples 1 to 3, a sintered metal plate 64 isplaced upon the top of the sample sheet 63, and they are fastenedtogether with a bolt 66 and a nut 67 through affixing member 65. Thiscup is left to stand in the atmosphere at a temperature of 25° C. andthe total weight of the cup is measured after 1 month. A reduction inthe weight of the cup per 24 hours is calculated and water vaporpermeability is calculated from the following expression water vaporpermeability [(g/24 hr·m²)]=M/(T·A) where A is a permeation area [m²], Tis a test time [day] and M is a weight reduction [g].

(2) The heat distortion temperature (load deflection temperature) of athermoplastic resin used as a continuous phase is measured at 0.45 MPain accordance with JIS K 7207.

(3) Measurement of Dew Point

The dew point is measured after the end of the following tests based onthe test standards of classes I to III (classification by accelerationdurability) specified in JIS R 3209.

class I: 7 days of moisture resistance and light resistance test+12cycles of cooling and heating repetition test class II: 14 days ofmoisture resistance and light resistance test+24 cycles of cooling andheating repetition test

class III: 42 days of moisture resistance and light resistance test+72cycles of cooling and heating repetition test

In the table, ∘ indicates that the dew point is −35° C. or less, Δindicates that the dew point is more than −35° C. and less than −30° C.and x indicates that the dew point is −30° C. or more.

(4) Dislocation at the Time of Processing

One glass sheet of the insulating glass produced in Examples andComparative Examples is fixed and a load of 8 kg is placed upon theother glass sheet to measure the amount of downward movement of theglass sheet that is loaded at a temperature of 50° C. A glass sheetwhich is moved 0.5 mm or less a day is expressed by ∘ and a glass sheetwhich is moved more than 0.5 mm is expressed by x.

As a result, the thermoplastic elastomer composition as in ComparativeExamples 1 and 2 which is produced from the rubber or thermoplasticresin with more water vapor permeability has low steam permeationresistance, and when such a thermoplastic elastomer composition is usedto form insulating glass, it has a high dew point due to steam entryinto the insulating glass through the seal.

Further, in Comparative Example 3, the amount of rubber was large andthe value of α₁ exceeded 1, so that the continuous phase formed byrubber and the dispersion phase formed by the resin were constructedinto layer. Since the rubber forming the continues phase has a low heatdistortion temperature, the rubber could not bear the load of glass atthe time of processing, resulting in dislocation.

TABLE 1 (part 1) Example 1 Example 2 Example 3 Example 4 Example 5Example 6 Example 7 matrix resin PET HDPE 30 30 30 30 30 30 50 PS rubbermodified butyl rubber 70 70 70 70 70 70 50 (Br-IPMS) EPDM IR barrierresin HDPE 10 20 vulcanizing system ZnO 3.5 3.5 3.5 3.5 3.5 3.5 2.5 zincstearate 1.4 1.4 1.4 1.4 1.4 1.4 1 stearic acid 0.7 0.7 0.7 0.7 0.7 0.70.5 sulfur NS phenol bromide age resistor RD 1.4 1.4 1.4 1.4 1.4 1.4 1moisture absorbing filler 50 50 50 zeolite 1 50 50 25 zeolite 2 50filler tackifier adhesion promoter (epoxysilane) talc 50 50 50 50 50 5050 rosin ester 50 50 50 50 50 50 50 silane coupling agent 2 0.5 2 2 2 22 steam permeability of resin*¹ 9 9 9 9 9 9 9 steam permeability ofrubber*¹ 82 82 82 82 82 82 82 heat deformation temperature of 112 112112 112 112 112 112 matrix resin (° C.) α₁ 0.93 0.93 0.93 0.93 0.93 0.930.40 α₁ — — — — 0.003 0.005 — η_(d)/η_(m) — — — — 3.8 3.8 —characteristic properties of material 38 37 38 38 25 16 24 steampermeability characteristic properties of multi-layer glass JIS R-3209class 1 ∘ ∘ ∘ ∘ ∘ ∘ ∘ class 2 ∘ ∘ ∘ ∘ ∘ ∘ ∘ class 3 ∘ Δ Δ ∘ ∘ ∘ ∘dislocation at the ∘ ∘ ∘ ∘ ∘ ∘ ∘ time of processing (part 2) ComparativeComparative Comparative Example 8 Example 9 Example 10 Example 1 Example2 Example 3 matrix resin PET 30 HDPE 70 30 30 5 PS 30 rubber modifiedbutyl rubber 30 70 95 (Br-IPMS) EPDM 70 70 70 IR barrier resin HDPEvulcanizing system ZnO 1.5 3.5 3.5 3.5 3.5 zinc stearate 0.6 1.4 0.7 1.4stearic acid 0.3 0.7 0.7 2.1 0.7 sulfur 1.4 Ns 0.7 phenol bromide 8.4age resistor RD 0.6 1.4 1.4 1.4 1.4 2 moisture absorbing filler zeolite1 50 50 50 50 50 50 zeolite 2 filler tackifier adhesion promoter(epoxysilane) talc 50 50 50 50 50 50 rosin ester 50 50 50 50 50 50silane coupling agent 2 2 2 2 2 2 steam permeability of resin*¹ 9 9 10 9840 9 steam permeability of rubber*¹ 82 157 82 1720 157 82 heatdeformation temperature of 112 112 191 112 88 — matrix resin (° C.) α₁0.03 0.93 0.98 0.90 0.89 7.6 α₁ — — — — — — η_(d)/η_(m) — — — — — —characteristic properties of 16 51 39 100 319 82 material steampermeability characteristic properties of multi-layer glass JIS R-3209class 1 ∘ ∘ ∘ ∘ Δ ∘ class 2 ∘ ∘ ∘ Δ x ∘ class 3 ∘ ∘ ∘ x x ∘ dislocationat the ∘ ∘ ∘ ∘ ∘ x time of processing *¹(g/m₂ · 24 h)

Examples 11 and 12

The thermoplastic elastomer composition of Example 1 as an inner layerand maleic acid modified EEA or ethylene-vinyl acetate saponifiedproduct as an outer layer were co-extruded at about 200° C. to form aspacer and insulating glass was produced in the same manner as inExample 1. The thickness of the obtained adhesive layer was about 20 μm.

The characteristic properties of the insulating glass were measured andevaluated in the same manner as in Example 1. Results are shown in Table2.

Example 13

A primer was prepared by dissolving an ethylene-vinyl acetate saponifiedproduct in toluene in a solid content of 10% This primer was coated on aglass sheet with a brush and left to stand for 15 minutes and theninsulating glass was produced in the same manner as in Example 1.Thereafter, the characteristic properties of the insulating glass wereevaluated in the same manner as in Example 1. Results are shown in Table2.

TABLE 2 Example 11 Example 12 Example 13 thermoplastic material ofmaterial of material of elastomer Example 1 Example 1 Example 1composition layer adhesive layer maleic acid ethylene-vinylethylene-vinyl modified EEA acetate acetate saponified saponifiedproduct product coating of double-layer double-layer primer coatingadhesive coextrusion coextrusion molding molding characteristicproperties of insulating glass JIS R-3209 class 1 ◯ ◯ ◯ class 2 ◯ ◯ ◯class 3 ◯ ◯ ◯ dislocation Δ ◯ ◯ at the time of ◯ ◯ ◯ processing<Components in Tables>

-   PET: J125 by Mitsui PET Co., Ltd.-   HDPE (matrix): Hizex 2100J by Mitsui Chemical Co., Ltd.-   PS: Stylon 666 R by Asahi Chemical Industry Co., Ltd.-   modified butyl rubber: Exxpro89-4 by Eccson Co., Ltd.-   EPDM: EPT 3045 by Mitsui Chemical Co., Ltd.-   IR: Nipole 2200 by Nippon Zeon Co., Ltd.-   HDPE (barrier resin): Ryubmer 5000 by Mitsui Chemical Co., Ltd.-   ZnO: zinc oxide No. 3 by Seido Kagaku Co., Ltd.-   zinc stearate: zinc stearate by Seido Kagaku Co., Ltd.-   stearic acid: bead stearic acid by NOF Corporation-   sulfur: powdery sulfur by Karuizawa Seirensho Co., Ltd.-   NS: Nokusera NS by Ohuchi Shinko Kagaku Co., Ltd.-   phenol bromide: Tackirol 250-1 by Taoka Kagaku Co., Ltd.-   RD: Antigen-RD-F by Sumitomo Chemical Co., Ltd.-   zeolite 1: Zeoram 4A by Tosoh Corporation-   zeolite 2: Zeoram 3 by Tosoh Corporation-   talc: Talc F by Nippon Talc Co., Ltd.-   rosin ester: Pensel AD by Arakawa Kagaku Co., Ltd.-   silane coupling agent: A-174 by Nippon Unicar Co., Ltd.-   maleic acid modified EEA: AR-201 by Mitsui-Dupont Polychemical Co.,    Ltd.-   ethylene-vinyl acetate saponified product: Dumiran C1550 by Takeda    Chemical Industries, Ltd.

Examples 14 to 16 and Comparative Example 4

A sealing material was produced according to formulations shown in Table3 below in the same manner as in Example 1. The steam permeabilities ofthe used resin and the used rubber were 9 g/24 hr·m² and 82 g/24 hr·m,respectively, and the water vapor permeability of the producedthermoplastic elastomer composition for sealing the insulating glass was38 g/24 hr·m².

TABLE 3 Example matrix resin HDPE 30 Rubber modified butyl rubber 70vulcanizing system ZnO 3.5 zinc stearate 1.4 stearic acid 0.7 Ageresistor RD 1.4 moisture absorbing filler zeolite 1 50 filler talc 50tackifier rosin ester 50 adhesive promoter ethylene-vinyl acetate 10copolymer saponified product

The sealing material produced by the above method had an MFR at 230° C.of 100 g/min. The produced sealing material pellets were injected into asimplified extruder, a nozzle was inserted into a space between twoglass sheets at 230° C., and the sealing material was charged into thespace at a delivery rate of 2,000 g/min to produce the followinginsulating glass production of insulating glass

-   -   size of glass sheet    -   thickness of glass sheet    -   type of glass sheet float glass    -   interval between glass sheets h: 6 mm    -   size of nozzle H: 5 mm        -   L: 15 mm        -   l: 5 mm        -   S₁: 5 mm        -   S₂: 2 mm

Table 4 below shows experimental results obtained by the comparison ofthe leveled surfaces of the sealing material W by the shape of thedischarge port of the nozzle body 11 and adhesion to the surface ofglass between Examples 14, 15 and 16 of the present invention and theprior art (Comparative Example 4).

As obvious from the experimental results, it has been found that theupper and lower leveled surfaces of the sealing material are better andthe adhesion of the sealing material to glass is better when the slideplate and the guide plate are provided at the leading end of the nozzlebody 11.

TABLE 4 Comparative Example 14 Example 15 Example 16 Example 4 shape ofdischarge port of nozzle no sliding portion upper and lower uppersurface Smooth Smooth almost smooth cut portion of leveled ⊚ ⊚ ∘ glassis not flat surfaces x lower surface Smooth almost smooth almost smoothbecomes wavy ⊚ ∘ ∘ x adhesion to glass surface adhered to almost adheredalmost adhered partly not entire surface to entire to entire adhered ⊚surface surface ∘ ∘ Δ

The thermoplastic elastomer composition of the present invention hasexcellent steam permeation resistance and heat distortion resistance andis suitable for use as the raw material of a sealing material and spacerfor insulating glass when a thermoplastic resin and rubber having a lowwater vapor permeability are used and the thermoplastic resin is used asa continuous phase.

The insulating glass of the present invention which uses thethermoplastic elastomer composition of the present invention as asealing material and spacer has excellent heat distortion resistance andan air layer having a sufficiently low dew point. Further, theinsulating glass of the present invention can be produced very easilybecause the number of production steps is much smaller than that of theconventional insulating glass.

Further, according to the process of the present invention, since asealing material is charged into a space between the peripheral portionsof glass sheets using a production nozzle having a slide plate whichslides along the peripheral portions of a plurality of glass sheets atthe top of the leading end portion of the nozzle body as describedabove, the sealing material can be efficiently paved in the spacebetween the peripheral portions of the glass sheets and can be directlyadhered to the glass sheets, and the sealing material at the peripheralportions of the glass sheets can be leveled to obtain good appearance,and efficient work can be carried out by reducing the number of workingsteps.

Further, the production nozzle of the present invention can beadvantageously used in this production process.

1. A process for producing insulating glass by charging a sealingmaterial having a predetermined width into a space between theperipheral portions of at least two glass sheets which are opposed toeach other in parallel at a predetermined interval to isolate a hollowlayer from the outside air, the process comprising the steps of:inserting in advance the leading end of a charging nozzle into the spacebetween the peripheral portions of a plurality of glass sheets;contacting a slide plate provided at the top of the leading end portionof the nozzle to the peripheral portions of the plurality of glasssheets; discharging the sealing material from the leading end of thenozzle body at a predetermined rate; and moving at least one of theglass sheets and the nozzle body relative to the other to charge thesealing material into the space between the peripheral portions of theglass sheets from the leading end of the nozzle.
 2. The process forproducing insulating glass according to claim 1, wherein the sealingmaterial at the peripheral portions of the plurality of glass sheets isleveled by the slide plate provided at the top of the leading endportion of the nozzle body and the lower side of the sealing material inthe space between the plurality of glass sheets is leveled by a guideplate provided at a lower end portion at the leading end of the nozzlebody when the sealing material is charged into the space between theperipheral portions of the glass sheets.
 3. The process for producinginsulating glass according to claim 1, wherein the sealing material andspacer comprises a thermoplastic elastomer composition produced from athermoplastic resin having a water vapor permeability of 100 g/m²·24 hor less (30 μm in thickness) and rubber having a water vaporpermeability of 300 g/m²·24 h or less (30 μm in thickness) whencrosslinked, said composition having a dispersion phase formed of arubber composition at least part of which is dynamically crosslinked inthe continuous phase of the thermoplastic resin.